Preparation of organic silicon compounds



Patented Aug. 9, 1949 [UNITED STATES PATENT OFFICE I rasrmrros gr rcamc silicon Arthur A. Levine, Niagara Falls, N. Y., assignor to E. I. duPont de Nemours & Complny, Wilmington, Del., a corporation of Delaware No Drawing. Application February 21, 1946,

Serial No. 849,389 r I 4 Claims. 1

This invention relates to the production of hydrocarbon-substituted silicon halides by reacting silicon and silicon-containing materials with hydrocarbon'halides. More particularly, this invention relates to a process for enhancing the reactivity of silicon and silicon-containing materials for use in the above-said reaction.

The production 1 of hydrocarbon-substituted silicon halides by reacting silicon and siliconcontaining substances with hydrocarbon halides at temperatures between 100 C. and 500 C. has been suggested heretofore in the patent application of Norman D. Scott, Serial No. 550.315, flied August 19, 1944, now abandoned, and in U. S. Patents Nos. 2,380,995 to 2,381,002, inclusive.

Many grades of commercial silicon donot react readily withv hydrocarbon halides. Furthermore, silicon often loses its reactivity for such halides.

It is an object of this invention to provide a process for enhancing and reviving the reactivity I,

of silicon and silicon-containing substances for their reaction with hydrocarbon halides.

It is another object of this invention to provide a process for enhancing, reviving, and maintaining the reactivity of silicon and silicon-containing substances simultaneously with their reaction withhydrocarbon halides.

'It is still another object ofthis invention to provide a process for enhancing and reviving the reactivity of silicon and silicon-containing substances before reacting the same with hydrocarbon halides.

Other objects of the invention will appear hereinafter.

The above objects may be accomplished, in general, by contacting the silicon-containing material withhydrogen fluoride. The hydrogen fluoride used in the treatment is preferably anhydrous, but may contain a small amount of water. Since the reaction between siliconic oxides and m, is a reversible one according to the equatreated with gaseous hydrogen fluoride at' any temperature above the boiling point of HF. Preferably, however, the treatment with gaseous hydrogen fluoride is carried out at a temperature above C., for example, between 100 C. and 500 0., so as to vaporize and remove any water which may be formed during the treatment.

If liquid hydrogen fluoride is used in treating boiling point'of HF, the length of the treatment period depends upon the reactivity and quantity of the silicon being treated, and the degree of reactivity desired. When gaseous hydrogen fluoride is employed, the length of the treatment period depends upon, in addition to the above conditions, the flow rate of the HF and the temperature of the system.

' Although the applicant, does not wish to be restricted to any theory regarding his invention, it is believed that the low reactivity of some silicon materials is due to the presence of SiO: or silicone compound on the surface of the silicon. These silicon oxide or silicone coatings prevent proper contact of the silicon with the hydrocarbon halide.

A short treatment of the silicon material having a low reactivity with the HF will form water and gaseous SiFl which are vaporized from the mate- Methyl chloride, CHaCl Methyl bromide, CHaBr Methylene chloride, CHzCla Ethyl chloride, C2H5C1 Allyl chloride,'CH==CHCHzCl Methyl iodide, CI-IsI Fluoroform, CHE: chloroform, CHCla Carbon tetrachloride, C014 Trichlorofluoromethane, CClaF Ethyl iodide, CzHsI 1,4-dlchlorobutane, C4HaC1 Ethylene dichloride, CzHiCl:

Vinylidene chloride, CH2=CC12 n-Propyl bromide, CaHvBr Iso-propyl chloride, CHzCHClCHs n-Butyl chloride, C4HaCl Cyclopentyl bromide, CsHeBl' The treatment of silicon material with HF will enhance the reactivity thereof for reaction with the above and other hydrocarbon halides.

The following examples are given to illustrate certain preferred processes for carrying out the present invention, it being understood, of course, that the invention is not to be limited to the details of the examples.

Example I Finely divided elemental silicon (100 mesh or finer) is dispersed, in the form of a dense cloud, within a cylindrical rotary reactor of about five liters volume by a continuous rotary motion of the reactor. Methyl chloride vapors are allowed to pass through this silicon cloud at a rate of one gram per minute and at a temperature maintained between 350 C. and 425 C. The vapor issuing from the reactor is condensed in a water-cooled condenser and fractionally distilled. Atmospheric distillation of the crude reaction products yields, in addition to recovered methyl chloride, trichlorosilicane, HSiCls, boiling point 31 to 33' C.; silicon tetrachloride, SiCh, boiling point 56 to 58 0.; monomethyl silicon trichloride, CHaSiCls, boiling point 65.5" C.; and dimethyl silicon dichloride, (CH3)2SiClz,- boiling point 69 C. Based upon unrecovered methyl chloride, a 66% conversion was realized,

indicating a fair initial reactivity of the silicon. i

Operations were discontinued overnight, but the system was maintained at reaction temperatures under an atmosphere of standard high purity nitrogen 3% oxygen). On the following morning, methyl chloride vapors were again introduced into the system, and the run was continued for six hours longer. methyl chloride was realized. Operations were discontinued overnight.

On the following morning, operations were resumed and a slow stream of anhydrous hydrogen fluoride was introduced in the system simultaneously with the methyl chloride. A reaction between the methyl chloride and silicon, as evidenced by the condensation of crude-product No reaction of the a 52% conversion. was realized -in a single pass. Since the silicon was previously shown to be unreactive to methyl chloride, the above conversion yield demonstrates the improved reactivity as caused by treatment of the silicon with hydrogen fluoride.

Example II Methyl chloride vapors were passed through a non-reactive silicon for a period of two hours at 350 C. to 400 C. in an apparatus similar to that described in Example. I.

The absence of condensate in the condenser indicated that very little or no reaction was being realized. Anhydrous hydrogen fluoride was then introduced into the system at a slow rate. After twenty minutes, the crude product vapors began to condense. It was found that as the flow of hydrogen fluoride was increased, the rate of prm duct condensation also increased, thus indicating that a greater conversion of methyl chloride was being realized. The run was terminated at the end of eight hours. A second run was made under similar conditions to evaluate the reactivity of the silicon. Based on methyl chloride consumed, 52.7% conversion was realized,

--thus showing that a considerable reactivity of the silicon had been accomplished.

The hydrogen fluoride need not be introduced into the system simultaneously with the hydrocarbon halide. If the silicon or silicon-containing substance has a low initial reactivity, or a low reactivity as a result of operation over an extended period of time, it may be treated with the hydrogen fluoride before it is reacted with the hydrocarbon halide.

Reference in the'speciflcation and claims to 'parts, proportions and percentages, unless otherwise specified, refers to parts, proportions, and

percentages by weight. V

Since it is obvious that many changes and modifications can be made in the above-described details without departing from the nature and spirit of the invention, it is to be understood that the invention is not to be limited to said details .except as set forth in the appended claims.

What is claimed is: a

1. In a process for the production of a hydro 2. In a process for the production of a hydrocarbon-substituted silicon halide by reacting silicon with a hydrocarbon halide the step of enhancing thereactivity of the silicon material vapors in the water-cooled condensen'was realized after three and one-quarter hours. At the end of four and one-half hours, the hydrogen fluoride flow was shut oil and the run was con tinued for one and three-quarter hours longer, during, which time the silicon remained reactive. Discontinuing operations overnight, the system was maintained under an atmosphere ofmethyl chloride vapors to prevent oxygen and'moistu're i'rom contacting the silicon.

The next day, a check run was made to determine the reactivity of the silicon. Methyl chloride vapors were passed into the system at 405 C. for six hours in the absence of hydrogen fluoride. Based on unrecovered methyl chloride,

having a relatively low reactivity which comprises contacting the same with gaseous anhydrous hydrogen fluoride. v

3. In a process for the production of a hydrocarbon-substituted silicon halide by reacting silicon with a hydrocarbon halide the step of enhancing the reactivity of the silicon material having a relatively low reactivity which comprises contacting the same with gaseous anhyleast C.

drous hydrogenfluoride at a temperature of'at '4. In a process for the production of a hydrocarbon substituted silicon halide by reacting silicon with a hydrocarbon halidethe'step of enhancing the reactivity of the silicon material having a relatively low reactivity which com- 6 prises contacting the same wlthllquld anhydrous Number Home DIM hydrogen fluoride. 2,380,998 Sprung us. 7, 194

ARTHUR A. LEVINE. 2,380,999 Sprung Aug; '1, 1945 2,381,000 Patnode Aug. 7, 1945 REFERENCES CITED 2,381,001 Patpode Aug. 7, 1945 2,381,002 Patnode Aug. 7, 1945 mm igillgvgangferences are of record in the 1383318 I Patnode Aug. 28' 1945 2,389,931 Reed et a1. Nov. 17, 1945 UNITED STATES PATENTS OTHER REFERENCES v I. $3333 s 51k ,Rochow', Jour. Amer. Chem. v01. 61 (1945),

2,380,998 Rochow Aug. '1, 1945 We 2,aao,9a7 Patnode Ana. '1. 1945 

